JP2007099922A - Ink for inkjet recording - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an inkjet recording ink having excellent storage stability and ejection stability, while achieving good color development on plain paper or glossy paper and high gloss and fixability on glossy paper. <P>SOLUTION: The inkjet recording ink comprises water and a pigment dispersed therein using a polymer having an acid number of ≥50 mgKOH/g and ≤120 mgKOH/g and a weight-average molecular weight of ≥20,000 and ≤120,000, and containing ≥50 wt.% benzyl acrylate, ≥10 wt.% styrene monomer and/or styrene macromonomer and ≤15 wt.% (meth)acrylic acid polymerized as a constitutional component of the polymer. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to an ink for ink jet recording having excellent storage stability and ejection stability, high color developability on plain paper and glossy paper, and high glossiness and fixability on glossy paper.

  As inks for ink jet recording, inks using dyes or pigments as colorants are currently in widespread use. In an ink using a pigment, a method using a surfactant as a means for dispersing the pigment in water (see Patent Document 1), a method using a dispersion polymer having a hydrophobic part and a hydrophilic part (see Patent Document 2), Alternatively, a method of coating the surface of the pigment with a polymer has been studied, and examples thereof include a method using a phase inversion emulsification reaction or an acid precipitation method (see Patent Document 3).

JP-A-1-301760 JP-A-6-306317 Japanese Patent Laid-Open No. 10-140065

  However, in any case, since a polymer containing styrene as a main constituent is used as a method for dispersing the pigment, the fixability is not so much, and yellowing is easily caused by long-term storage of the printed matter. Further, in the normal case, when a substance having a hydrophilic part and a hydrophobic part such as a surfactant or glycol ether is present, there is a problem that adsorption / desorption tends to occur and storage stability is inferior. Conventional water-based inks require a substance having a hydrophilic part and a hydrophobic part such as a surfactant and glycol ether in order to reduce bleeding on paper. Ink that does not use these substances has insufficient permeability to paper, and there is a problem that the type of paper is limited in order to perform uniform printing, which tends to cause a reduction in the printed image.

  Further, for example, additives for improving printing quality (acetylene glycol surfactants, acetylene alcohol surfactants, silicon surfactants, di (tri) ethylene glycol monobutyl ether, or 1,2) are added to conventional dispersions. -Alkylene glycol or a mixture thereof), long-term storage stability cannot be obtained, and in the case of pigment ink, the re-dissolvability is poor, so that the ink is dried and easily clogged with the nozzles of the inkjet head, However, there is a problem that a material such as an adhesive used for the substance constituting the material is attacked to lower the adhesive strength and deteriorate the ejection stability.

  In addition, in the pigment ink dispersed by such a general dispersant, the residue of the dispersant remains in the ink, and the dispersant does not contribute sufficiently to the dispersion and is detached from the pigment and has a high viscosity. There was a problem that it ended up When the viscosity is increased, the amount of the coloring material such as pigment is limited, and there is a problem that sufficient print quality cannot be obtained particularly on plain paper.

  The ink for inkjet recording of the present invention comprises water and at least 50% by weight or more of benzyl acrylate, 10% by weight or more of styrene monomer and / or styrene macromonomer, and 15% by weight or less (meth) acrylic acid as a polymer component. And a pigment dispersed using a polymer having a weight average molecular weight of 20,000 to 120,000 and having an acid value of 50 mgKOH / g to 120 mgKOH / g.

  The ink for ink jet recording of the present invention is excellent in storage stability and ejection stability, and provides ink for ink jet recording having high color developability on plain paper and glossy paper, high gloss on glossy paper, and fixability. Has a good effect.

  The ink for ink-jet recording of the present invention is excellent in storage stability and ejection stability, has high color development on plain paper and glossy paper, has fixing properties in addition to sufficient gloss on glossy paper, This is due to the result of intensive studies in view of the demand for characteristics such as excellent ink ejection stability.

  The ink for inkjet recording of the present invention comprises water and at least 50% by weight or more of benzyl acrylate, 10% by weight or more of styrene monomer and / or styrene macromonomer, and 15% by weight or less (meth) acrylic acid as a polymer component. And a pigment dispersed using a polymer having a weight average molecular weight of 20,000 to 120,000 and having an acid value of 50 mgKOH / g to 120 mgKOH / g.

  The present invention is characterized by using a polymer in which 50% by weight or more of benzyl acrylate and 15% by weight or less of (meth) acrylic acid are polymerized. If benzyl acrylate is less than 50% by weight, the fixability is lowered, so the preferred range is 50% by weight or more. However, the case of less than 50% by weight is not denied, and more preferably 50% by weight or more. Preferably it is 60 weight% or more. Further, the polymer of the present invention is characterized by polymerization with 15% by weight or less of (meth) acrylic acid as a constituent component of the polymer, but if it exceeds 15% by weight, the color developability of the inkjet recording ink on plain paper Tend to decrease. However, polymerization exceeding 15% by weight is not denied, and a more preferable range is 10% by weight or less. When methacrylic acid and acrylic acid are compared, it is more preferable to use acrylic acid from the viewpoint of fixability.

  Furthermore, the present invention is characterized by using 10% by weight or more of a styrene monomer and / or a styrene macromonomer as a constituent component of the polymer, thereby improving the fixing property and glossiness. If it is 10% by weight or less, the fixability deteriorates. More preferably, it is 15% by weight or more.

  In the present invention, the polymer in which the pigment is dispersed preferably has a weight average molecular weight of 20,000 or more and 200,000 or less. If the weight average molecular weight is less than 20,000, the long-term storage stability, thermal stability and fixability as an ink for ink jet recording deteriorate, and if it exceeds 200,000, the viscosity as an ink for ink jet recording increases and the dispersion stability. Tends to be worse, and the ejection stability tends to be lower.

  The pigment used in the present invention is, for example, carbon black (CI pigment black 7) such as furnace black, lamp black, acetylene black, channel black, copper oxide, iron oxide (C CI pigment black 11), metals such as titanium oxide, organic pigments such as aniline black (CI pigment black 1), etc., but carbon having a relatively low specific gravity for ink jet recording is difficult to settle in water. Black is preferred. Further, for color use, C.I. I. Pigment Yellow 1 (Fast Yellow G), 3, 12 (Disazo Yellow AAA), 13, 14, 17, 24, 34, 35, 37, 42 (Yellow Iron Oxide), 53, 55, 74, 81, 83 (Disazo Yellow HR), 93, 94, 95, 97, 98, 100, 101, 104, 108, 109, 110, 117, 120, 128, 138, 153, 180, C.I. I. Pigment Red 1, 2, 3, 5, 17, 22 (Brilliant First Scarlet), 23, 31, 38, 48: 2 (Permanent Red 2B (Ba)), 48: 2 (Permanent Red 2B (Ca)), 48 : 3 (Permanent Red 2B (Sr)), 48: 4 (Permanent Red 2B (Mn)), 49: 1, 52: 2, 53: 1, 57: 1 (Brilliant Carmine 6B), 60: 1, 63: 1, 63: 2, 64: 1, 81 (Rhodamine 6G rake), 83, 88, 101 (Bengara), 104, 105, 106, 108 (Cadmium red), 112, 114, 122 (Quinacridone magenta), 123, 146, 149, 166, 168, 170, 172, 177, 178, 179, 185, 190, 193, 202, 209, 219, 254, . I. Pigment violet 19, C.I. I. Pigment Blue 1, 2, 15 (phthalocyanine blue R), 15: 1, 15: 2, 15: 3 (phthalocyanine blue G), 15: 4, 15: 6 (phthalocyanine blue E), 16, 17: 1, 56 , 60, 63, C.I. I. Pigment Green 1, 4, 7, 8, 10, 17, 18, 36, etc. can be used.

  The added amount of the pigment is preferably 0.5 to 30% by weight, more preferably 1.0 to 12% by weight. If the addition amount is 0.5% by weight or less, the print density cannot be secured, and if the addition amount is 30% by weight or more, the viscosity of the ink increases and structural viscosity is generated in the viscosity characteristics, and the ejection stability of the ink from the inkjet head Tends to get worse.

  The polymer used for dispersion of the pigment in the present invention is a commercially available styrene- (meth) acrylic acid copolymer, styrene- (meth) acrylic acid- (meth) acrylic acid ester copolymer, polyethylene glycol ( A combination of one or more selected from a (meth) acrylate- (meth) acrylic acid copolymer, a vinyl acetate-maleic acid copolymer, a styrene-maleic acid copolymer, and the like can also be used. However, it is preferable that at least 80% or more is a polymer obtained by copolymerization of acrylate and acrylic acid. Examples of the acrylate include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, hexyl acrylate, cyclohexyl acrylate, octyl acrylate, lauryl acrylate, 2-ethylhexyl acrylate, 2-ethylhexyl carbitol acrylate, phenol EO-modified acrylate, N-vinyl pyrrolidone, Commercially available acrylates such as isobornyl acrylate, benzyl acrylate, paracumylphenol EO-modified acrylate, and 2-hydroxyethyl-3-phenoxypropyl acrylate can be used. Further, ω-carboxy-polycaprolactone monoacrylate, phthalic acid monohydroxyethyl acrylate, acrylic acid dimer or the like can be used instead of acrylic acid.

  Next, examples of the polymerizable monomer having a (meth) acryloyl group include monofunctional (meth) acrylates, polyfunctional (meth) acrylates, and mixtures thereof. Examples of monofunctional (meth) acrylates include 2- Methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-phenoxyethyl (meth) arylate, ethoxydiethylene glycol (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, ethylene oxide adduct of nonylphenol (meth) Acrylates, propylene oxide adducts of nonylphenol (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, dicyclopente (Meth) acrylate, isobornyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl Examples include (meth) acrylate.

  Moreover, it is preferable that the dispersion method using the polymer used by this invention is phase inversion emulsification. By using the phase inversion emulsification method, the ink becomes stable and the color developability of plain paper is improved.

  The ink of the present invention is 2,4,7,9-tetramethyl-5-decyne-4,7-diol, 3,6-dimethyl-4-octyne-3,6-diol, 2,4,7,9. 0.05 or more of one or more selected from alkylene oxide adducts of tetramethyl-5-decyne-4,7-diol and alkylene oxide adducts of 3,6-dimethyl-4-octyne-3,6-diol It is preferable that it comprises 1% by weight or more. If the added amount is less than 0.05% by weight, bleeding on plain paper increases, which is not preferable. On the other hand, if it exceeds 1% by weight, the storage stability as an ink for ink jet recording deteriorates, and long-term storage becomes difficult. More preferably, it is 0.1 wt% or more and 0.7 wt%. The 2,4,7,9-tetramethyl-5-decyne-4,7-diol, 3,6-dimethyl-4-octyne-3,6-diol, 2,4,7,9-tetramethyl An alkylene oxide adduct of -5-decyne-4,7-diol is commercially available, Surfynol 104, Surfinol 82, Surfinol 2502, Surfinol 420, Surfinol 440, Surfinol 465, manufactured by Nissin Chemical Co., Ltd. It can be obtained as Surfynol 485, acetylenol EOO, acetylenol E40, acetylenol E100 manufactured by Kawaken Fine Chemical Co., Ltd.

  The ink of the present invention preferably contains 1,2-alkylene glycol. Among the 1,2-alkylene glycols, 1,2-hexanediol and 4-methyl-1,2-pentanediol are particularly preferable. By using the pigment dispersion of the present invention and further using these, ink jet recording ink can be discharged. Stability is improved and bleeding is reduced when printing on plain paper.

  The ink of the present invention is one kind selected from di (tri) ethylene glycol monobutyl ether, (di) propylene glycol monobutyl ether, di (tri) ethylene glycol monopentyl ether and di (tri) ethylene glycol monohexyl ether. It is preferable to comprise the above. By using the pigment dispersion of the present invention and further using these glycol ethers, bleeding when printed on plain paper by the inkjet method is further reduced, and the printing quality is improved.

  Furthermore, the ink of the present invention preferably comprises 2-butyl-2-ethyl-1,3-propanediol, and the pigment dispersion of the present invention is used to make 2-butyl-2-ethyl-1,3 -Further use of propanediol improves glossiness on glossy paper and improves color developability on plain paper.

  The polymer of the present invention has a carboxyl group, and preferably contains triethanolamine and / or tripropanolamine as a counter ion. By using triethanolamine and / or tripropanolamine, clogging of ink for ink jet recording hardly occurs even in a dry state.

  Similarly, in order to prevent clogging of the inkjet head, the ink preferably contains one or more selected from glycerin, trimethylolethane, trimethylolpropane, tetrasaccharide, pentasaccharide and hexasaccharide.

  In the polymer polymerization method of the present invention, an alcohol solvent, a ketone solvent, an ether solvent, or a glycol ether solvent can be used as a solvent. However, since it is an aqueous pigment dispersion, it is necessary to be able to remove the above-mentioned solvent later. Therefore, the following can be used as such a solvent. Examples of the alcohol solvent include methanol, ethanol, isopropanol, 1-butanol, tertiary butanol, isobutanol, diacetone alcohol and the like. Examples of the ketone solvent include acetone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, and cyclohexanone. Examples of the ether solvent include dibutyl ether, tetrahydrofuran, dioxane and the like. Furthermore, examples of the glycol ethers include ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, and butyl cellosolve.

  Moreover, as a radical polymerization initiator for polymerizing a polymer, t-butyl peroxy (2-ethylhexanoate), di-t-butyl peroxide, t-butyl peroxybenzoate, t-butyl peroxyoct Organic peroxides such as ate, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), dimethyl-2,2′-azobisbutyrate, 2, Azo compounds such as 2′-azobis (2-methylbutyronitrile), potassium persulfate, sodium persulfate, and the like can be used, but are not limited to these, and start other than the above as long as radical polymerization is possible. An agent can also be used. The amount of radical polymerization initiator used is preferably 0.01 mol% or more and 5 mol% or less with respect to the monomer used in the polymerization. The polymerization temperature is not particularly limited, but is usually in the range of 30 to 100 ° C, and preferably in the range of 40 to 90 ° C. When the polymerization temperature is too low, it is necessary to take a long time for the polymerization of the monomer, and in some cases, the polymerization rate may decrease and a large amount of monomer may remain.

  The ink of the present invention further contains a dispersant, a surface tension adjusting agent or a penetrating agent (surfactant), a wetting / drying preventing agent, an antiseptic, a bactericidal agent, a pH adjusting agent, a rust preventing agent, a moisturizing agent, and the like. These additives may be used. These may be used alone or in combination of two or more.

  The high-pressure disperser used for the preparation of the pigment dispersion used in the ink of the present invention is not particularly limited, but a medialess disperser is preferably used from the viewpoint of contamination contamination and dispersion stability. Examples thereof include a fluidizer (Microfluidics), an optimizer (Sugino Machine), a wet jet mill (Genus), and a nanomizer (Nanomizer).

  The pressure at the time of dispersing with the above-described high-pressure disperser may be any as long as it can reach the desired pigment particle diameter, but is preferably 100 MPa to 300 MPa. If it is less than 100 MPa, the dispersed particle size tends to be large, it takes time to disperse, and unless the number of passes is extremely increased, a stable dispersion is unlikely to be economical. Moreover, when it exceeds 300 MPa, it is easy to become overdispersed, and it is difficult to obtain the stability of the dispersion. If the desired pigment particle diameter cannot be reached, the dispersion may be carried out by increasing the number of dispersions or increasing the pressure within the aforementioned pressure range.

  In addition, as a method for producing the ink for ink jet recording of the present invention, an alkali solution is added to the polymer composition of the ink for ink jet recording that has been polymerized and heated, and then the solvent is removed, and ion exchange water or the like is used. You may use the polymer composition solution of the inkjet recording ink substituted.

  Further, the solvent of the ink-jet recording ink, which has been polymerized, is removed by distillation under reduced pressure, the solid matter of the ink-jet recording ink polymer obtained is crushed, and ion-exchanged water, an alkali solution, etc. are added and heated. You may use the polymer solution of the ink for inkjet recording obtained by melt | dissolving. In this case, thereafter, it is not necessary to remove the organic solvent and the like from the obtained pigment dispersion.

  Examples of the alkali used in the alkali solution include tertiary alkyl alkanolamines such as triethanolamine, tripropanolamine, and ethyldiethanolamine, and inorganic bases such as sodium hydroxide, potassium hydroxide, and lithium hydroxide. .

(Example)
The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to these examples, and various modifications can be made without departing from the gist of the present invention.

  The inside of a 2000 ml separable flask equipped with a stirrer, a reflux tube, a thermometer, and a dropping funnel was purged with nitrogen, and then 200.0 parts by weight of diethylene glycol monomethyl ether was placed in the separable flask and heated to 80 ° C. while stirring. . Subsequently, 200.0 parts by weight of diethylene glycol monomethyl ether, 363.0 parts by weight of benzyl acrylate, 120 parts by weight of styrene, 50.4 parts by weight of acrylic acid and t-butylperoxy (2-ethylhexanoate) are added to the dropping funnel. 8 parts by weight was added and reacted dropwise at 80 ° C. over 4 hours in a separable flask. After completion of dropping, the mixture was kept at 80 ° C. for 1 hour, 0.8 parts by weight of t-butylperoxy (2-ethylhexanoate) was added, and the reaction was further carried out at 80 ° C. for 1 hour. Thereafter, diethylene glycol monomethyl ether was removed by distillation under reduced pressure. Then, 600.0 parts by weight of methyl ethyl ketone was added to obtain a polymer composition solution having a resin solid content of 50%. A part of the polymer composition solution thus obtained was taken and dried for 1 hour in an oven at 105 ° C., and then the acid value of the obtained polymer was 65 mgKOH / g, and the weight average molecular weight was 33000. Met.

  Next, 3.0 parts by weight of a 30% aqueous sodium hydroxide solution is added to 120.0 parts by weight of the polymer composition solution thus prepared, and the mixture is stirred with a high-speed disper for 5 minutes. Further, Cyanine Blue G- 480.0 parts by weight of 500 pure-A (CI PB15: 1; manufactured by Sanyo Dye Co., Ltd.) was added, and the mixture was stirred with a high-speed disper for 1 hour to obtain a pigment dispersion slurry. Then, the pigment dispersion slurry was continuously dispersed 10 times at a pressure of 200 MPa with an ultrahigh pressure homogenizer (Microfluidizer, manufactured by Mizuho Kogyo Co., Ltd.) to obtain a pigment dispersion.

  Further, methyl ethyl ketone and a part of water were distilled off from the pigment dispersion thus obtained by vacuum distillation using an evaporator, and centrifuged at 5000 rpm for 30 minutes with a centrifuge (05P-21, manufactured by Hitachi, Ltd.). After the separation, ion-exchanged water was added so that the pigment concentration was 15% by weight to prepare a pigment dispersion. And it filtered under pressure using a 5.0 micrometer membrane filter (made by Advantech). Then, the ink for inkjet recording of the ink composition example 1 shown in Table 2 was created.

  Instead of 50.4 parts by weight of acrylic acid, 13.2 parts of methacrylic acid, 36.5 parts by weight of acrylic acid, 120 parts of styrene 80 parts of styrene and styrene macromonomer AS-6S (manufactured by Toagosei Co., Ltd.) Except for changing to 40 parts, the same operation as in Example 1 was carried out, and an ink for inkjet recording of Composition Example 2 shown in Table 2 was produced. Further, after taking a part of the polymer composition solution and drying it for 1 hour with a high-temperature dryer at 105 ° C., the acid value of the polymer of the obtained ink for ink jet recording is 60 mgKOH / g, and the weight average molecular weight is 31000. Met.

  Implemented except that instead of 50.4 parts by weight of acrylic acid, 42.6 parts by weight of acrylic acid was used and 120 parts of styrene were changed to 80 parts of styrene and 40 parts of styrene macromonomer AS-6S (manufactured by Toagosei Co., Ltd.). In the same manner as in Example 1, an inkjet recording ink of Composition Example 3 shown in Table 2 was prepared. Further, after taking a part of the polymer composition solution and drying it for 1 hour with an oven at 105 ° C., the acid value of the polymer of the obtained ink for ink jet recording is 55 mgKOH / g, and the weight average molecular weight is 45000. Met.

  Implemented except that instead of 50.4 parts by weight of acrylic acid, 77.5 parts by weight of acrylic acid was used and 120 parts of styrene were changed to 80 parts of styrene and 40 parts of styrene macromonomer AS-6S (manufactured by Toagosei Co., Ltd.). In the same manner as in Example 1, an inkjet recording ink of Composition Example 4 shown in Table 2 was prepared. Further, a part of the polymer composition solution was taken and dried for 1 hour with a high-temperature dryer at 105 ° C., and then the acid value of the polymer of the obtained ink for ink jet recording was 100 mgKOH / g, and the weight average molecular weight was 27000. Met.

  Implemented except that 93.0 parts by weight of acrylic acid was used instead of 50.4 parts by weight of acrylic acid, 120 parts of styrene was changed to 80 parts of styrene and 40 parts of styrene macromonomer AS-6S (manufactured by Toagosei Co., Ltd.). In the same manner as in Example 1, an inkjet recording ink of Composition Example 5 shown in Table 2 was produced. Further, after taking a part of the polymer composition solution and drying for 1 hour with a high-temperature dryer at 105 ° C., the acid value of the polymer of the obtained ink for ink jet recording is 120 mgKOH / g, and the weight average molecular weight is 33000. Met.

  Table 2 shows the same procedure as in Example 1 except that 480.0 parts by weight of Cyanine G-500 pure-A having a pigment concentration of 25% by weight was replaced by Monarch 880 (CI PBk7: manufactured by Cabot). An ink for ink jet recording of composition example 13 shown in FIG. Further, a part of the polymer composition solution was taken and dried for 1 hour with a high-temperature dryer at 105 ° C., and then the acid value of the polymer of the obtained ink for ink jet recording was 65 mgKOH / g, and the weight average molecular weight was 32000. Met.

  The same procedure as in Example 2 was conducted except that Monarch 880 (CI PBk7: manufactured by Cabot) was used instead of 480.0 parts by weight of Cyanine G-500 pure-A having a pigment concentration of 25% by weight. An ink for ink jet recording having the composition example 14 shown was prepared. In addition, after taking a part of the polymer composition solution and drying it with a high-temperature dryer at 105 ° C. for 1 hour, the acid value of the polymer of the obtained ink for ink jet recording is 60 mgKOH / g, and the weight average molecular weight is 30000. Met.

  Instead of 120.0 parts by weight of Cyanine G-500 pure-A, the same as Example 1 except that 120.0 parts by weight of Pigment Violet GC227-A (CI PV19; manufactured by Sanyo Pigment Co., Ltd.) was used. Then, an ink for ink jet recording of Composition Example 19 shown in Table 2 was prepared. Further, a part of the polymer composition solution was taken and dried for 1 hour with a high-temperature dryer at 105 ° C., and then the acid value of the polymer of the obtained ink for ink jet recording was 65 mgKOH / g, and the weight average molecular weight was 32000. Met.

  The same procedure as in Example 2 was conducted except that 120.0 parts by weight of Pigment Violet GC227-A was used in place of 120.0 parts by weight of Cyanine G-500 pure-A. Inkjet recording of Composition Example 20 shown in Table 2 Ink was made. Further, after taking a part of the polymer composition solution and drying it for 1 hour with a high-temperature dryer at 105 ° C., the acid value of the polymer of the obtained ink for ink jet recording is 60 mgKOH / g, and the weight average molecular weight is 31000. Met.

  Instead of 120.0 parts by weight of Cyanine G-500 pure-A, 120.0 parts by weight of Fast Yellow 7413-A (CI PY74; manufactured by Sanyo Dye Co., Ltd.) was used in the same manner as in Example 1. Then, an ink for ink jet recording of Composition Example 25 shown in Table 2 was prepared. Further, a part of the polymer composition solution was taken and dried for 1 hour in a high-temperature dryer at 105 ° C., and then the acid value of the polymer of the obtained ink for ink jet recording was 65 mgKOH / g, and the weight average molecular weight was 33000. Met.

  Instead of 120.0 parts by weight of Cyanine G-500 pure-A, 120.0 parts by weight of Fast Yellow 7413-A (CI PY74; manufactured by Sanyo Color Co., Ltd.) was used in the same manner as in Example 2. Then, an ink for inkjet recording of Composition Example 26 shown in Table 2 was prepared. Further, after taking a part of the polymer composition solution and drying it for 1 hour with a high-temperature dryer at 105 ° C., the acid value of the polymer of the obtained ink for ink jet recording is 60 mgKOH / g, and the weight average molecular weight is 31000. Met.

(Comparative Example 1)
An ink jet recording ink of Composition Example 6 shown in Table 2 was prepared in the same manner as in Example 1 except that 363.0 parts by weight of benzyl acrylate and 120 parts by weight of styrene were used instead of 483.0 parts by weight of benzyl acrylate. . Further, after taking a part of the polymer composition solution and drying for 1 hour with a high-temperature dryer at 105 ° C., the acid value of the polymer of the obtained ink for ink jet recording is 65 mgKOH / g, and the weight average molecular weight is 27000. Met.

(Comparative Example 2)
An ink for inkjet recording of Composition Example 7 shown in Table 2 was produced in the same manner as in Example 1 except that 116.3 parts by weight of acrylic acid was used instead of 50.4 parts by weight of acrylic acid. Moreover, after taking a part of polymer composition solution and drying for 1 hour with a 105 degreeC high heat dryer, the acid value of the polymer of the obtained ink for inkjet recording is 150 mgKOH / g, and the weight average molecular weight is 32000. Met.

(Comparative Example 3)
An ink for inkjet recording of Composition Example 8 shown in Table 2 was prepared in the same manner as in Example 1 except that 155.0 parts by weight of acrylic acid was used instead of 50.4 parts by weight of acrylic acid. Further, after taking a part of the polymer composition solution and drying for 1 hour with a high-temperature dryer at 105 ° C., the acid value of the polymer of the obtained ink for ink jet recording is 200 mgKOH / g, and the weight average molecular weight is 27000. Met.

(Comparative Example 4)
The same as Example 1 except that t-butylperoxy (2-ethylhexanoate) was changed to 4.8 parts by weight and t-butylperoxy (2-ethylhexanoate) was changed to 20.0 parts by weight. Then, an ink for ink jet recording of Composition Example 9 shown in Table 2 was prepared. Further, after taking a part of the polymer composition solution and drying it for 1 hour with a high-temperature dryer at 105 ° C., the acid value of the polymer of the obtained ink for ink jet recording is 65 mgKOH / g, and the weight average molecular weight is 10,000. Met.

(Comparative Example 5)
The same as Example 2 except that 15.0 parts by weight of t-butylperoxy (2-ethylhexanoate) was used instead of 4.8 parts by weight of t-butylperoxy (2-ethylhexanoate). The ink for inkjet recording of the composition example 10 shown in Table 2 was produced. Further, after taking a part of the polymer composition solution and drying it for 1 hour with an oven at 105 ° C., the acid value of the polymer of the obtained ink for ink jet recording is 60 mgKOH / g, and the weight average molecular weight is 17000. Met.

(Comparative Example 6)
Example 1 except that 4.8 parts by weight of t-butylperoxy (2-ethylhexanoate) was replaced with 3.1 parts by weight of t-butylperoxy (2-ethylhexanoate). The ink for inkjet recording of the composition example 11 shown in Table 2 was produced. Further, after taking a part of the polymer composition solution and drying it with a high-temperature dryer at 105 ° C. for 1 hour, the acid value of the polymer of the obtained ink for ink jet recording was 65 mgKOH / g, and the weight average molecular weight was 120,000. Met.

(Comparative Example 7)
Implemented except that instead of 50.4 parts by weight of acrylic acid, 23.3 parts by weight of acrylic acid was used and 120 parts of styrene were changed to 80 parts of styrene and 40 parts of styrene macromonomer AS-6S (manufactured by Toagosei Co., Ltd.). In the same manner as in Example 1, an ink for inkjet recording of Composition Example 12 shown in Table 2 was prepared. Moreover, after taking a part of polymer composition solution and drying for 1 hour with a 105 degreeC high temperature dryer, the acid value of the polymer of the obtained ink for inkjet recording is 30 mgKOH / g, and the weight average molecular weight is 32000. Met.

(Comparative Example 8)
Cyanine G G-500 pure-A Instead of 480.0 parts by weight, Monarch 880 (CI PBk7: manufactured by Cabot) was replaced with 480.0 parts by weight. An ink for ink jet recording of Composition Example 15 shown was prepared. Further, a part of the polymer composition solution was taken and dried for 1 hour with a high-temperature dryer at 105 ° C., and then the acid value of the polymer of the obtained ink for ink jet recording was 130 mgKOH / g, and the weight average molecular weight was 27000. Met.

(Comparative Example 9)
Cyanine Blue G-500 pure-A Instead of 480.0 parts by weight, Monarch 880 (CI PBk7: manufactured by Cabot) was replaced with 480.0 parts by weight. The ink for inkjet recording of the composition example 16 shown was produced. Further, after taking a part of the polymer composition solution and drying it for 1 hour with an oven at 105 ° C., the acid value of the polymer of the obtained ink for ink jet recording is 60 mgKOH / g, and the weight average molecular weight is 17000. Met.

(Comparative Example 10)
Cyanine G G-500 pure-A Instead of 480.0 parts by weight, Monarch 880 (CI PBk7: manufactured by Cabot) was replaced with 480.0 parts by weight. An ink for ink-jet recording having the composition example 17 shown was prepared. Moreover, after taking a part of polymer composition solution and drying for 1 hour with a 105 degreeC high heat dryer, the acid value of the polymer of the obtained ink for inkjet recording is 65 mgKOH / g, and the weight average molecular weight is 120,000. Met.

(Comparative Example 11)
Cyanine Blue G-500 pure-A Instead of 480.0 parts by weight, the same procedure as in Comparative Example 7 was carried out except that Monarch 880 (CI PBk7: manufactured by Cabot) was changed to 480.0 parts by weight. The ink for inkjet recording of the composition example 18 shown was produced. Moreover, after taking a part of polymer composition solution and drying for 1 hour with a 105 degreeC high temperature dryer, the acid value of the polymer of the obtained ink for inkjet recording is 30 mgKOH / g, and the weight average molecular weight is 32000. Met.

(Comparative Example 12)
The same procedure as in Comparative Example 1 was performed except that 480.0 parts by weight of Pigment Violet GC227-A was used instead of 480.0 parts by weight of Cyanine G-500 pure-A. Inkjet recording of Composition Example 21 shown in Table 2 Ink was made. Further, a part of the polymer composition solution was taken and dried for 1 hour with a high-temperature dryer at 105 ° C., and then the acid value of the polymer of the obtained ink for ink jet recording was 130 mgKOH / g, and the weight average molecular weight was 27000. Met.

(Comparative Example 13)
The same procedure as in Comparative Example 5 was conducted except that Pigment Violet GC227-A 480.0 parts by weight was used instead of 480.0 parts by weight of Cyanine G-500 pure-A. Inkjet recording of Composition Example 22 shown in Table 2 Ink was made. Moreover, after taking a part of polymer composition solution and drying for 1 hour with a 105 degreeC high heat dryer, the acid value of the polymer of the obtained ink for inkjet recording is 60 mgKOH / g, and the weight average molecular weight is 16000. Met.

(Comparative Example 14)
The same procedure as in Comparative Example 6 was conducted except that Pigment Violet GC227-A 480.0 parts by weight was used instead of 480.0 parts by weight of Cyanine G-500 pure-A. Inkjet recording of Composition Example 23 shown in Table 2 Ink was made. Further, after taking a part of the polymer composition solution and drying for 1 hour with a high-temperature dryer at 105 ° C., the acid value of the polymer of the obtained ink for ink jet recording is 60 mgKOH / g, and the weight average molecular weight is 120,000. Met.

(Comparative Example 15)
The same procedure as in Comparative Example 7 was conducted except that Pigment Violet GC227-A 480.0 parts by weight was used instead of 480.0 parts by weight of Cyanine G-500 pure-A 48. Inkjet recording of Composition Example 24 shown in Table 2 Ink was made. Further, after taking a part of the polymer composition solution and drying it for 1 hour with an oven at 105 ° C., the acid value of the polymer of the obtained ink for ink jet recording is 30 mgKOH / g, and the weight average molecular weight is 32000. Met.

(Comparative Example 16)
The same procedure as in Comparative Example 1 was conducted except that 480.0 parts by weight of Fast Yellow 7413-A was used instead of 480.0 parts by weight of Cyanine G-500 pure-A. Inkjet recording of Composition Example 27 shown in Table 2 Ink was made. Further, a part of the polymer composition solution was taken and dried for 1 hour with a high-temperature dryer at 105 ° C., and then the acid value of the polymer of the obtained ink for ink jet recording was 130 mgKOH / g, and the weight average molecular weight was 27000. Met.

(Comparative Example 17)
The same procedure as in Comparative Example 5 was conducted except that 480.0 parts by weight of Fast Yellow 7413-A was used instead of 480.0 parts by weight of Cyanine G-500 pure-A. Inkjet recording of Composition Example 28 shown in Table 2 Ink was made. Further, after taking a part of the polymer composition solution and drying it for 1 hour with an oven at 105 ° C., the acid value of the polymer of the obtained ink for ink jet recording is 60 mgKOH / g, and the weight average molecular weight is 17000. Met.

(Comparative Example 18)
The same procedure as in Comparative Example 6 was conducted except that 480.0 parts by weight of Fast Yellow 7413-A was used instead of 480.0 parts by weight of Cyanine G-500 pure-A. Inkjet recording of Composition Example 29 shown in Table 2 Ink was made. Moreover, after taking a part of polymer composition solution and drying for 1 hour with a 105 degreeC high heat dryer, the acid value of the polymer of the obtained ink for inkjet recording is 65 mgKOH / g, and the weight average molecular weight is 120,000. Met.

(Comparative Example 19)
The same procedure as in Comparative Example 7 was conducted except that 480.0 parts by weight of Fast Yellow 7413-A was used instead of 480.0 parts by weight of Cyanine G-500 pure-A. Inkjet recording of Composition Example 30 shown in Table 2 Ink was made. Further, after taking a part of the polymer composition solution and drying it for 1 hour with an oven at 105 ° C., the acid value of the polymer of the obtained ink for ink jet recording is 30 mgKOH / g, and the weight average molecular weight is 31000. Met.

(Evaluation test 1: Evaluation method of abrasion resistance)
The inks for inkjet recording according to Examples 1 to 11 and Comparative Examples 1 to 19 were solid-printed on PM photo paper (Seiko Epson Corporation) with an inkjet printer (EM-930C, Seiko Epson Corporation), and a test specimen Got. The print mode was paper: photo print paper, print quality: photo, color correction: none, print direction: bidirectional. Thereafter, a fixing property evaluation test was performed by rubbing the test specimen with a line marker on which 300 g of fruit juice was applied. The fixability evaluation test is performed by a method of observing the degree of ink peeling when the printed surface and the back surface are moved at a speed of 1 m / s by overlapping with a load of 300 g using the above test body (PM photographic paper). It was. In Table 2, S does not peel at all even if moved 3 times, AA does not peel at all even if moved 2 times, but slightly peels off when moved 3 times, A does not peel at all Although there is no peeling, slight peeling occurs when moved twice, B is peeling slightly, C is peeling and transferred to the back surface, and D is considerably peeled and transferred to the back surface.

(Evaluation Test 2: Evaluation Method for Colorability of Plain Paper)
The inkjet recording inks according to Examples 1 to 11 and Comparative Examples 1 to 19 were solid-printed on XeroxP paper (manufactured by Fuji Xerox Co., Ltd.) using an inkjet printer (EM-930C, manufactured by Seiko Epson Corporation), and tested. Get the body. The print mode was paper: plain paper, print quality: super fine, color correction: none, print direction: bidirectional. And it is by measuring the OD value of each color using GRETAGMACBETH SPECTROSCANSP50 (made by Gretag (USA)). The results are shown in Table 1 as OD values.

(Evaluation Test 3: Glossiness Evaluation Method)
The inks for inkjet recording according to Examples 1 to 11 and Comparative Examples 1 to 19 were solid-printed on PM photo paper (Seiko Epson Corporation) with an inkjet printer (EM-930C, Seiko Epson Corporation), and a test specimen Got. The print mode was paper: photo print paper, print quality: photo, color correction: none, print direction: bidirectional. The 20 degree gloss of this test specimen was measured with a gloss meter (HG-268, manufactured by Suga Test Instruments Co., Ltd.). The results are shown in Table 1.

(Evaluation Test 4: Particle Size Evaluation Method)
The average particle diameter of the particles in the inks for inkjet recording according to Examples 1 to 11 and Comparative Examples 1 to 19 was measured with a laser particle size analyzer (Zeta Sizer 3000, manufactured by Malvern, UK).

(Evaluation Test 5: Evaluation Method for Storage Stability)
The initial viscosity of the pigment dispersion of the ink jet recording ink used in Examples 1 to 11 and Comparative Examples 1 to 19 and the viscosity after standing at 70 ° C. for 1 week were measured using a rolling ball viscometer (AMVn, Anton Pearl ( (Germany)). The results are shown in Table 1 as storage stability: viscosity (mPa · s) / initial viscosity (mPa · s) after standing at 70 ° C. for 1 week.

  Table 1 also shows the monomer composition, the polymerization initiator and the pigment, and the ink composition for ink jet recording that were used when the ink for ink jet recording was produced.

The abbreviations shown in Tables 1 and 2 are as follows.
BZA: benzyl acrylate AA: acrylic acid MAA: methacrylic acid BPEH: t-butylperoxy (2-ethylhexanoate)
ST: Styrene STM: Styrene macromonomer AS-6S (manufactured by Toagosei Co., Ltd.)
PBk7: C.I. I. Pigment Black 7 (carbon black)
PB15: 1: C.I. I. Pigment Blue 15: 1 (trichlorophthalocyanine)
PV19: C.I. I. Pigment Violet 19 (Quinacridone)
PY74: C.I. I. Pigment Yellow 74 (Condensed Azo Pigment)
DEGmBE: diethylene glycol monobutyl ether TEGmBE: triethylene glycol monobutyl ether PGmBE: propylene glycol monobutyl ether DPGmBE: dipropylene glycol monobutyl ether BEPD: 2-butyl-2-ethyl-1,3-propanediol 1,2-HD: 1, 2-Hexanediol TMP: Trimethylolpropane

  As can be seen from the results in Tables 1 and 2, when the inks for ink jet recording according to Examples 1 to 11 are used, the evaluation tests 1 to 5 are all good results, but the ink jet recordings according to Comparative Examples 1 to 19 are used. When the ink for use is used, good results are not obtained in any of the evaluation tests 1 to 5 or a plurality of items.

Claims (5)

  Water and at least 50% by weight or more of benzyl acrylate, 10% by weight or more of styrene monomer and / or styrene macromonomer, and 15% by weight or less of (meth) acrylic acid are polymerized as a polymer component, and 50 mgKOH / g or more and 120 mgKOH are polymerized. And a pigment dispersed using a polymer having a weight average molecular weight of 20000 or more and 120,000 or less and having an acid value of / g or less.   0.05% to 1% by weight of 2,4,7,9-tetramethyl-5-decyne-4,7-diol and 2,4,7,9-tetramethyl-5-decyne-4,7 The ink for inkjet recording according to claim 1, comprising at least one selected from alkylene oxide adducts of diols.   The ink for inkjet recording according to claim 1, comprising 1,2-alkylene glycol.   The ink for inkjet recording according to any one of claims 1 to 3, comprising at least one selected from di (tri) ethylene glycol monobutyl ether and (di) propylene glycol monobutyl ether.   The ink for inkjet recording according to claim 1, comprising 2-butyl-2-ethyl-1,3-propanediol.